Method for producing silicone hydrogel contact lenses

ABSTRACT

The present invention generally relates to a method for producing inherently wettable silicone hydrogel contact lenses with a robusteness of lens shape and having relatively high oxygen permeability, relatively high equilibrium water content and relatively low elastic modulus.

This application claims the benefit under 35 USC § 119 (e) of U.S.provisional application No. 62/516,205 filed 7 Jun. 2017, hereinincorporated by reference in its entirety.

The present invention generally relates to a method for producingnaturally wettable silicone hydrogel contact lenses with a robustness oflens shape.

BACKGROUND

Silicone hydrogel (SiHy) contact lenses, which are made of a hydrated,crosslinked polymeric material that contains silicone and a certainamount of water within the lens polymer matrix at equilibrium, areincreasingly becoming popular, because they have minimal adverse effectson corneal health due to their relatively high oxygen permeability. But,incorporation of silicone in a contact lens material can haveundesirable effects on the hydrophilicity and wettability of SiHycontact lenses, because silicon is hydrophobic and has a great tendencyto migrate onto the lens surface being exposed to air. Contact lensesmanufacturers have made a great effort in developing SiHy contact lenseshaving a hydrophilic and wettable surface.

One interesting approach for rending SiHy contact lenses wettablewithout post curing surface treatment is the incorporation of monomericwetting agents (e.g., N-vinylpyrrolidone, N-vinyl-N-methyl acetamide, orthe like) in a lens formulation for making SiHy contact lens as proposedin U.S. Pat. Nos. 6,867,245, 7,268,198, 7,540,609, 7,572,841, 7,750,079,7,934,830, 8,231,218, 8,367,746, 8,445,614, 8,481,662, 8,487,058,8,513,325, 8,703,891, 8,820,928, 8,865,789, 8,937,110, 8,937,111,9,057,821, 9,057,822, 9,121,998, 9,125,808, 9,140,825, 9,140,908,9,156,934, 9,164,298, 9,170,349, 9,188,702, 9,217,813, 9,296,159,9,322,959, 9,322,960, 9,360,594, 9,529,119. Although this approach mayprovide fresh (unused) SiHy lenses with adequately hydrophilic surfaces,there are some limitations. For example, the higher oxygen permeabilityof a SiHy contact lens could be achieved according to this approach, butat the expense of its equilibrium water content and atomic Si percentageat lens surface. Typically, relatively-lower equilibrium water contentand relatively-higher atomic Si percentage go with higher oxygenpermeability in tandem. Further, it may also have one or more of thefollowing disadvantages: slightly-high haziness; a relatively-highersurface silicone content; susceptibility to form dry spots and/orhydrophobic surface areas created due to air exposure,drying-rehydrating cycles, shearing forces of the eyelids, siliconemigration, and/or partial failure to prevent silicone from exposure; andnot-adequate lubricity.

SUMMARY OF THE INVENTION

The invention is related to a method for producing naturally wettablesilicone hydrogel contact lenses with a robusteness of lens shape. Themethod comprises the steps of: preparing a polymerizable compositionwhich is clear at room temperature and optionally but preferably at atemperature of from about 0 to about 4° C., wherein the polymerizablecomposition comprises (a) at least one siloxane-containing vinylicmonomer including 0 to 10 first H-donor moieties, (b) at least one firstpolysiloxane vinylic crosslinker which has a number average molecularweight of from about 3000 Daltons to about 80,000 Daltons and comprises(i) two terminal (meth)acryloyl groups, (ii) at least one polysiloxanesegment comprising dimethylsiloxane units and hydrophilized siloxaneunits each having one methyl substituent and one monovalent C₄-C₄₀organic radical substituent having one or more second H-donor moieties,and (iii) from 0 to 20 third H-donor moieties which are integral partsof molecular structures outside of the polysiloxane segment, (c) atleast one hydrophilic N-vinyl amide monomer, (d) a C₁-C₄ alkyl(meth)acrylate in an amount for increasing the robusteness of lens shapeof silicone hydrogel contact lenses produced from the polymerizablecomposition relative to a control polymerizable composition free ofC₁-C₄ alkyl (meth)acrylate, (e) optionally at least one secondpolysiloxane vinylic crosslinker having 0 to 35 fourth H-donor moieties,and (f) at least one free radical initiator, wherein the first andsecond polysiloxane vinylic crosslinker are different from each other,wherein the first, second, third and fourth H-donor moieties independentof one another are hydroxyl groups, carboxyl groups, amino groups of—NHR^(o), amino linkages of —NH—, amide linkages of —CONH—, urethanelinkages of —OCONH—, or combinations thereof, wherein R^(o) is H or aC₁-C₄ alkyl, wherein the polymerizable composition comprises at least8.8 mmoles of component (c) per gram of all components (a), (b) and (e)in total and at least 0.11 meqs of all the first, second, third andfourth H-donor moieties in total per gram of component (c); introducingthe polymerizable composition into a lens mold; curing thermally oractinically the polymerizable composition in the lens mold to form asilicone hydrogel contact lens, wherein the silicone hydrogel contactlens has an oxygen permeability of at least 50 barrers, an elasticmodulus of from about 0.2 MPa to about 1.5 MPa, and an equilibrium watercontent of from about 40% to about 70% and is inherently wettable ascharacterized by having a water-break-up-time of at least 10 seconds anda water contact angle by captive bubble of about 80 degrees or lesswithout being subjected to any post-curing surface treatment.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 schematically shows how to measure water-break-up time of acontact lens.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Generally, the nomenclatureused herein and the laboratory procedures are well known and commonlyemployed in the art. Conventional methods are used for these procedures,such as those provided in the art and various general references. Wherea term is provided in the singular, the inventors also contemplate theplural of that term. The nomenclature used herein and the laboratoryprocedures described below are those well-known and commonly employed inthe art. Also, as used in the specification including the appendedclaims, reference to singular forms such as “a,” “an,” and “the” includethe plural, and reference to a particular numerical value includes atleast that particular value, unless the context clearly dictatesotherwise. “About” as used herein means that a number referred to as“about” comprises the recited number plus or minus 1-10% of that recitednumber.

“Contact Lens” refers to a structure that can be placed on or within awearer's eye. A contact lens can correct, improve, or alter a user'seyesight, but that need not be the case. A contact lens can be of anyappropriate material known in the art or later developed, and can be asoft lens, a hard lens, or a hybrid lens. A “silicone hydrogel contactlens” refers to a contact lens comprising a silicone hydrogel bulk(core) material.

A “soft contact lens” refers to a contact lens which has an elasticmodulus (i.e., Young's modulus) of less than 2.5 MPa.

A “hydrogel” or “hydrogel material” refers to a crosslinked polymericmaterial which has three-dimensional polymer networks (i.e., polymermatrix), is insoluble in water, but can hold at least 10% by weight ofwater in its polymer matrix when it is fully hydrated (or equilibrated).

A “silicone hydrogel” refers to a silicone-containing hydrogel obtainedby copolymerization of a polymerizable composition comprising at leastone silicone-containing monomer or at least one silicone-containingmacromer or at least one crosslinkable silicone-containing prepolymer.

As used in this application, the term “non-silicone hydrogel” refers toa hydrogel that is theoretically free of silicon.

“Hydrophilic,” as used herein, describes a material or portion thereofthat will more readily associate with water than with lipids.

A “vinylic monomer” refers to a compound that has one sole ethylenicallyunsaturated group, is soluble in a solvent, and can be polymerizedactinically or thermally.

The term “room temperature” refers to a temperature of about 21° C. toabout 27° C.

The term “soluble”, in reference to a compound or material in a solvent,means that the compound or material can be dissolved in the solvent togive a solution with a concentration of at least about 0.02% by weightat room temperature.

The term “insoluble”, in reference to a compound or material in asolvent, means that the compound or material can be dissolved in thesolvent to give a solution with a concentration of less than 0.005% byweight at room temperature.

As used in this application, the term “ethylenically unsaturated group”is employed herein in a broad sense and is intended to encompass anygroups containing at least one >C═C<group. Exemplary ethylenicallyunsaturated groups include without limitation (meth)acryloyl

allyl, vinyl, styrenyl, or other C═C containing groups.

The term “terminal (meth)acryloyl group” refers to one (meth)acryloylgroup at one of the two ends of the main chain (or backbone) of anorganic compound as known to a person skilled in the art.

The term “(meth)acrylamide” refers to methacrylamide and/or acrylamide.

The term “(meth)acrylate” refers to methacrylate and/or acrylate.

As used herein, “actinically” in reference to curing, crosslinking orpolymerizing of a polymerizable composition, a prepolymer or a materialmeans that the curing (e.g., crosslinked and/or polymerized) isperformed by actinic irradiation, such as, for example, UV/visibleirradiation, ionizing radiation (e.g. gamma ray or X-ray irradiation),microwave irradiation, and the like. Thermal curing or actinic curingmethods are well-known to a person skilled in the art.

A “hydrophilic vinylic monomer”, as used herein, refers to a vinylicmonomer which as a homopolymer typically yields a polymer that iswater-soluble or can absorb at least 10 percent by weight of water.

A “hydrophobic vinylic monomer”, as used herein, refers to a vinylicmonomer which as a homopolymer typically yields a polymer that isinsoluble in water and can absorb less than 10% by weight of water.

A “blending vinylic monomer” refers to a vinylic monomer capable ofdissolving both hydrophilic and hydrophobic components of apolymerizable composition to form a solution.

An “acrylic monomer” refers to a vinylic monomer having one sole(meth)acryloyl group.

An “N-vinyl amide monomer” refers to an amide compound having a vinylgroup (—CH═CH₂) that is directly attached to the nitrogen atom of theamide group.

A “macromer” or “prepolymer” refers to a compound or polymer thatcontains ethylenically unsaturated groups and has a number averagemolecular weight of greater than 700 Daltons.

As used in this application, the term “vinylic crosslinker” refers to anorganic compound having at least two ethylenically unsaturated groups. A“vinylic crosslinking agent” refers to a vinylic crosslinker having amolecular weight of 700 Daltons or less.

As used in this application, the term “polymer” means a material formedby polymerizing/crosslinking one or more monomers or macromers orprepolymers or combinations thereof.

As used in this application, the term “molecular weight” of a polymericmaterial (including monomeric or macromeric materials) refers to thenumber average molecular weight unless otherwise specifically noted orunless testing conditions indicate otherwise.

A “polysiloxane segment” refers to a polymer chain consisting of atleast three consecutively- and directly-linked siloxane units (divalentradical) each independent of one another having a formula of

in which R₁′ and R₂′ are two substituents independently selected fromthe group consisting of C₁-C₁₀ alkyl, C₁-C₄-alkyl- orC₁-C₄-alkoxy-substituted phenyl, C₁-C₁₀ fluoroalkyl, C₁-C₁₀ fluoroether,C₆-C₁₈ aryl radical, -alk-(OC₂H₄)_(γ1)—OR^(o) (in which alk is C₁-C₆alkyl diradical, R^(o) is H or C₁-C₄ alkyl and γ1 is an integer from 1to 10), a C₂-C₄₀ organic radical having at least one functional groupselected from the group consisting of hydroxyl group (—OH), carboxylgroup (—COOH), —NR₃′R₄′, amino linkages of —NR₃′-, amide linkages of—CONR₃′-, amide of —CONR₃′R_(a)′, urethane linkages of —OCONH—, andC₁-C₄ alkoxy group, or a linear hydrophilic polymer chain, in which R₃′and R₄′ independent of each other are hydrogen or a C₁-C₁₅ alkyl.

A “polysiloxane vinylic crosslinker” refers to a compound comprising atleast one polysiloxane segment and at least twoethylenically-unsaturated groups.

A “linear polysiloxane vinylic crosslinker” refers to a compoundcomprising a main chain which includes at least one polysiloxane segmentand is terminated with one ethylenically-unsaturated group at each ofthe two ends of the main chain.

A “chain-extended polysiloxane vinylic crosslinker” refers to a compoundcomprising at least two ethylenically-unsaturated groups and at leasttwo polysiloxane segments each pair of which are linked by one divalentradical.

The term “fluid” as used herein indicates that a material is capable offlowing like a liquid.

As used in this application, the term “clear” in reference to apolymerizable composition means that the polymerizable composition is atransparent solution or liquid mixture (i.e., having a lighttransmissibility of 85% or greater, preferably 90% or greater in therange between 400 to 700 nm).

The term “alkyl” refers to a monovalent radical obtained by removing ahydrogen atom from a linear or branched alkane compound. An alkyl group(radical) forms one bond with one other group in an organic compound.

The term “alkylene divalent group” or “alkylene diradical” or “alkyldiradical” interchangeably refers to a divalent radical obtained byremoving one hydrogen atom from an alkyl. An alkylene divalent groupforms two bonds with other groups in an organic compound.

The term “alkoxy” or “alkoxyl” refers to a monovalent radical obtainedby removing the hydrogen atom from the hydroxyl group of a linear orbranched alkyl alcohol. An alkoxy group (radical) forms one bond withone other group in an organic compound.

In this application, the term “substituted” in reference to an alkyldiradical or an alkyl radical means that the alkyl diradical or thealkyl radical comprises at least one substituent which replaces onehydrogen atom of the alkyl diradical or the alkyl radical and isselected from the group consisting of hydroxyl (—OH), carboxyl (—COOH),—NH₂, sulfhydryl (—SH), C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ alkylthio(alkyl sulfide), C₁-C₄ acylamino, C₁-C₄ alkylamino, di-C₁-C₄ alkylamino,and combinations thereof.

A free radical initiator can be either a photoinitiator or a thermalinitiator. A “photoinitiator” refers to a chemical that initiates freeradical crosslinking/polymerizing reaction by the use of light. A“thermal initiator” refers to a chemical that initiates radicalcrosslinking/polymerizing reaction by the use of heat energy.

The intrinsic “oxygen permeability”, Dk_(i), of a material is the rateat which oxygen will pass through a material. As used in thisapplication, the term “oxygen permeability (Dk)” in reference to ahydrogel (silicone or non-silicone) or a contact lens means a correctedoxygen permeability (Dk_(c)) which is measured at about 34-35° C. andcorrected for the surface resistance to oxygen flux caused by theboundary layer effect according to the procedures described in Example 1of U.S. Pat. Appl. Pub. No. 2012-0026457 A1. Oxygen permeability isconventionally expressed in units of barrers, where “barrer” is definedas [(cm³ oxygen)(mm)/(cm²)(sec)(mm Hg)]×10⁻¹⁰.

The “oxygen transmissibility”, Dk/t, of a lens or material is the rateat which oxygen will pass through a specific lens or material with anaverage thickness of t [in units of mm] over the area being measured.Oxygen transmissibility is conventionally expressed in units ofbarrers/mm, where “barrers/mm” is defined as [(cm³ oxygen)/(cm²)(sec)(mmHg)]×10⁻⁹.

“Ophthalmically compatible”, as used herein, refers to a material orsurface of a material which may be in intimate contact with the ocularenvironment for an extended period of time without significantlydamaging the ocular environment and without significant user discomfort.

The term “modulus” or “elastic modulus” in reference to a contact lensor a material means the tensile modulus or Young's modulus which is ameasure of the stiffness of a contact lens or a material. A personskilled in the art knows well how to determine the elastic modulus of asilicone hydrogel material or a contact lens. For example, allcommercial contact lenses have reported values of elastic modulus. Itcan be measured as described in Example 1.

“UVA” refers to radiation occurring at wavelengths between 315 and 380nanometers; “UVB” refers to radiation occurring between 280 and 315nanometers; “Violet” refers to radiation occurring at wavelengthsbetween 380 and 440 nanometers.

“UVA transmittance” (or “UVA % T”), “UVB transmittance” or “UVB % T”,and “violet-transmittance” or “Violet % T” are calculated by thefollowing formula

${{UVA}\mspace{14mu} \% \mspace{14mu} T} = {\frac{{Average}\mspace{14mu} \% \mspace{14mu} {Transmission}\mspace{14mu} {between}\mspace{14mu} 315\mspace{14mu} {nm}\mspace{14mu} {and}\mspace{14mu} 380\mspace{14mu} {nm}}{{Luminescence}\mspace{14mu} \% \mspace{14mu} T} \times 100}$${{UVB}\mspace{14mu} \% \mspace{14mu} T} = {\frac{{Average}\mspace{14mu} \% \mspace{14mu} {Transmission}\mspace{14mu} {between}\mspace{14mu} 280\mspace{14mu} {nm}\mspace{14mu} {and}\mspace{14mu} 315\mspace{14mu} {nm}}{{Luminescence}\mspace{14mu} \% \mspace{14mu} T} \times 100}$${{Violet}\mspace{14mu} \% \mspace{14mu} T} = {\frac{{Average}\mspace{14mu} \% \mspace{14mu} {Transmission}\mspace{14mu} {between}\mspace{14mu} 380\mspace{14mu} {nm}\mspace{14mu} {and}\mspace{14mu} 440\mspace{14mu} {nm}}{{Luminescence}\mspace{14mu} \% \mspace{14mu} T} \times 100}$

in which is Luminescence % T is determined by the following formula

Luminescence % T=Average % Transmission between 780-380 nm.

An “H-donor moiety” refers to a functional group which comprises ahydrogen atom capable of forming a hydrogen bond with another functionalgroup. Examples of H-donor moieties include without limitation hydroxylgroup, amide group of —CONHR^(o), amide linkage of —CONH—, urethanelinkage of —OCONH—, urea linkage of —HNCONH—, carboxyl group of —COOH,amino groups of —NHR^(o), amino linkages of —NH—, and combinationsthereof, wherein R^(o) is H or a C₁-C₄ alkyl.

The term “inherently wettable” in reference to a silicone hydrogelcontact lens means that the silicone hydrogel has water-break-up-time(WBUT) of about 10 seconds or more and a water contact angle by captivebubble (WCA_(cb)) of about 80 degree or less without being subjected toany surface treatment after the silicone hydrogel contact lens is formedby thermally or actinically polymerizing (i.e., curing) a siliconehydrogel lens formulation. In accordance with the invention, WBUT andWCA_(cb) are measured according to the procedures described in Example1.

“Surface modification” or “surface treatment”, as used herein, meansthat an article has been treated in a surface treatment process (or asurface modification process) prior to or posterior to the formation ofthe article, in which (1) a coating is applied to the surface of thearticle, (2) chemical species are adsorbed onto the surface of thearticle, (3) the chemical nature (e.g., electrostatic charge) ofchemical groups on the surface of the article are altered, or (4) thesurface properties of the article are otherwise modified. Exemplarysurface treatment processes include, but are not limited to, a surfacetreatment by energy (e.g., a plasma, a static electrical charge,irradiation, or other energy source), chemical treatments, the graftingof hydrophilic vinylic monomers or macromers onto the surface of anarticle, mold-transfer coating process disclosed in U.S. Pat. No.6,719,929, the incorporation of wetting agents into a lens formulationfor making contact lenses proposed in U.S. Pat. Nos. 6,367,929 and6,822,016, reinforced mold-transfer coating disclosed in U.S. Pat. No.7,858,000, and a hydrophilic coating composed of covalent attachment orphysical deposition of one or more layers of one or more hydrophilicpolymer onto the surface of a contact lens disclosed in U.S. Pat. Nos.8,147,897 and 8,409,599 and U.S. Pat. Appl. Pub. Nos. 2011-0134387 A1,2012-0026457 A1 and 2013-0118127 A1.

“Post-curing surface treatment”, in reference to a silicone hydrogelbulk material or a SiHy contact lens, means a surface treatment processthat is performed after the silicone hydrogel bulk material or the SiHycontact lens is formed by curing (i.e., thermally or actinicallypolymerizing) a SiHy lens formulation. A “SiHy lens formulation” refersto a polymerizable composition that comprises all necessarypolymerizable components for producing a SiHy contact lens or a SiHylens bulk material as well known to a person skilled in the art.

The invention is generally related to a method for producinginherently-wettable SiHy contact lenses with a relatively high oxygenpermeability, a desired water content (e.g., from about 40% to about 70%by weight), and a relatively low elastic modulus (e.g., from about 0.2MPa to about 1.5 MPa). As reported in two commonly-owned copendingpatent applications filed on the same date with this application, thisinvention is partly based on the discovery that inherently-wettable SiHycontact lenses can be formed from a SiHy lens formulation (i.e., apolymerizable composition) that comprises a polysiloxane vinyliccrosslinker (“Di-PDMS”) having H-donor moieties (“H-D”), asiloxane-containing vinylic monomer (“mono-PDMS”) with or withoutH-donor moieties, a N-vinyl amide monomer (“NVA”) (e.g.,N-vinylpyrrolidone, N-vinyl-N-methyl acetamide, or the like), andoptionally other silicone-containing polymerizable component(s) with orwithout H-donor moieties, provided that the SiHy lens formulationcomprise about 8.8 mmoles or more of all N-vinyl amide monomer(s)(“NVA”) per gram of all the silicone-containing polymerizable components(i.e.

$\left. {\frac{\lbrack{NVA}\rbrack \mspace{14mu} {mmole}}{\left( {\left\lbrack {{mono}\text{-}{PDMS}} \right\rbrack + \left\lbrack {{di}\text{-}{PDMS}} \right\rbrack} \right)\mspace{14mu} g} = {8.8\mspace{14mu} {mmole}\text{/}g}} \right)$

and about 0.11 milliequivalents (“meq”) or more of the H-donor moietiesper gram of all N-vinyl amide monomer(s) ((i.e.,

$\left. \left. {\frac{\left\lbrack {H\text{-}D} \right\rbrack \mspace{14mu} {meq}}{\lbrack{NVA}\rbrack \mspace{14mu} g} = {0.11\mspace{14mu} {m{eq}}\text{/}g}} \right) \right),$

which are contributed from the polysiloxane vinylic crosslinker and thesiloxane-containing vinylic monomer, per gram of the N-vinyl amidemonomer. The resultant SiHy lenses not only can be inherently wettable,but also can have a combination of the desired contact lens propertiesincluding relatively high oxygen permeability, relatively high watercontent, relatively low modulus, and relatively-low surface atomic Sipercentage. This invention is also partly based on the discovery that,by adding a sufficient amount of methyl methacrylate in a SiHy lensformulation for making inherently wetable SiHy contact lenses, therobusteness of lens shape of resultant SiHy contact lenses can beincreased compared to those obtained from a control lens formulationwithout methyl methacrylate. It is found that when a lens formulationhaving less than 5 weight parts units of methyl macrylate, SiHy contactlenses cast-molded from such a lens formulation may have macroscopicallywinkled lens surface that in turn causes a non-round lens shape, namely,severe defects in lens morphology. When the concentration methylmethacrylate in the lens formulation is increased to 7 weight part unitsor higher, no resultant SiHy contact lenses can have any more winkledlens lens surface and non-round lens shape. By increasing therobusteness of lens shape, the production yield can be increased and theproduction cost can be decreased. This invention is further partly basedon the discovery that methyl methacrylate can also function as delensaid for facilitating removal of inherently wettable SiHy contact lensesin a dry state (i.e., the lenses without contacting with water or anysolvent after being cast molded) from molds, and thereby may reduce lensdamages during demolding and delensing process and the production cost.

The invention, in one aspect, provides a method for producing naturallywettable silicone hydrogel contact lenses with a robusteness of lensshape, comprising the steps of: preparing a polymerizable compositionwhich is clear at room temperature and optionally (but preferably) at atemperature of from about 0 to about 4° C., wherein the polymerizablecomposition comprises (a) at least one siloxane-containing vinylicmonomer including 0 to 10 first H-donor moieties, (b) at least one firstpolysiloxane vinylic crosslinker which has a number average molecularweight of from about 3000 Daltons to about 80,000 Daltons (preferablyfrom about 4000 to about 40000 Daltons, more preferably from about 5000to about 20000 Daltons) and comprises (i) two terminal (meth)acryloylgroups, (ii) at least one polysiloxane segment comprisingdimethylsiloxane units and hydrophilized siloxane units each having onemethyl substituent and one monovalent C₄-C₄₀ organic radical substituenthaving one or more second H-donor moieties, and (iii) from 0 to 20 thirdH-donor moieties which are integral parts of molecular structuresoutside of the polysiloxane segment, (c) at least one hydroany philicN-vinyl amide monomer, (d) a C₁-C₄ alkyl (meth)acrylate in an amount forincreasing the robusteness of lens shape of silicone hydrogel contactlenses produced from the polymerizable composition relative to a controlpolymerizable composition free of C₁-C₄ alkyl (meth)acrylate, (e)optionally at least one second polysiloxane vinylic crosslinker having 0to 35 fourth H-donor moieties, and (f) at least one free radicalinitiator, wherein the first and second polysiloxane vinyliccrosslinkers are different from each other, wherein the first, second,third and fourth H-donor moieties independent of one another arehydroxyl groups, carboxyl groups, amino groups of —NHR^(o), aminolinkages of —NH—, amide linkages of —CONH—, urethane linkages of—OCONH—, or combinations thereof, wherein R^(o) is H or a C₁-C₄ alkyl,wherein the polymerizable composition comprises at least 8.8 (preferablyat least 9.0, more preferably at least 9.2, even more preferably atleast 9.6) mmoles of component (c) per gram of all components (a), (b)and (e) in total and at least 0.11 (preferably at least 0.15, morepreferably at least 0.20, even more preferably at least 0.25) meqs ofall the first, second, third and fourth H-donor moieties in total pergram of component (c); introducing the polymerizable composition into alens mold; curing thermally or actinically the polymerizable compositionin the lens mold to form a silicone hydrogel contact lens, wherein thesilicone hydrogel contact lens has an oxygen permeability of at least 50barrers (preferably at least 60 barrers, more preferably at least 70barrers, even more preferably at least 80 barrers, most preferably atleast 100 barrers), an elastic modulus of from about 0.2 MPa to about1.5 MPa (preferably from about 0.3 MPa to about 1.2 MPa, more preferablyfrom about 0.4 MPa to about 1.0 MPa), and an equilibrium water contentof from about 40% to about 70% (preferably from about 43% to about 65%,more preferably from about 45% to about 60%) by weight and is inherentlywettable as characterized by having a water-break-up-time of at least 10seconds (preferably at least 15 seconds, more preferably at least 20seconds) and a water contact angle by captive bubble of about 80 degreesor less (preferably about 75 degrees or less, more preferably about 70degrees or less, even more preferably about 65 degrees or less) withoutbeing subjected to any post-curing surface treatment.

Any suitable siloxane-containing vinylic monomers can be used in theinvention.

One class of preferred siloxane containing vinylic monomers ismono-(meth)acryloyl-terminated monoalkyl-terminated polysiloxanes.Examples of mono-(meth)acryloyl-terminated monoalkyl-terminatedpolysiloxanes include without limitation α-(meth)acryloxypropylterminated ω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-(meth)acryloxy-2-hydroxypropyloxypropyl terminated ω-butyl (orω-methyl) terminated polydimethylsiloxane,α-(2-hydroxyl-methacryloxypropyloxypropyl)-ω-butyl-decamethylpentasiloxane,α-[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl]-terminated ω-butyl(or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloxy-propyloxy-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloxyisopropyloxy-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloxybutyloxy-2-hydroxypropyloxypropyl]-terminated ω-butyl(or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloxyethylamino-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloxypropylamino-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloxybutylamino-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-(meth)acryloxy(polyethylenoxy)-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[(meth)acryloxy-2-hydroxypropyloxy-ethoxypropyl]-terminated ω-butyl(or ω-methyl) terminated polydimethylsiloxane,α-[(meth)acryloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated ω-butyl(or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloxy-2-hydroxypropyl-aminopropyl]-terminated ω-butyl (orω-methyl) terminated polydimethylsiloxane,α-[(meth)acryloxy-2-hydroxypropyloxy-(polyethylenoxy)propyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-(meth)acryloylamidopropyloxypropyl terminated ω-butyl (or ω-methyl)terminated polydimethylsiloxane,α-N-methyl-(meth)acryloylamidopropyloxypropyl terminated ω-butyl (orω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acrylamidoethoxy-2-hydroxypropyloxypropyl]-terminated ω-butyl(or ω-methyl) polydimethylsiloxane,α-[3-(meth)acrylamidopropyloxy-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acrylamidoisopropyloxy-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloylamido-2-hydroxypropyloxypropyl] terminated ω-butyl(or ω-methyl) polydimethylsiloxane,α-[3-[N-methyl-(meth)acryloylamido]-2-hydroxypropyloxypropyl]terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,N-methyl-N′-(propyltetra(dimethylsiloxy)dimethylbutylsilane)(meth)acrylamide,N-(2,3-dihydroxypropane)-N′-(propyltetra(dimethylsiloxy)dimethylbutylsilane)(meth)acrylamide,(meth)acryloylamidopropyltetra(dimethylsiloxy)dimethylbutylsilane, andmixtures thereof. Mono-(meth)acryloyl-terminated, monoalkyl-terminatedpolysiloxanes can be obtained from commercial suppliers (e.g.,Shin-Etsu, Gelest, etc.) or prepared according to procedures describedin U.S. Pat. Nos. 6,867,245, 8,415,405, 8,475,529, 8,614,261, and9,217,813 or by reacting a hydroxyalkyl (meth)acrylate or(meth)acrylamide or a (meth)acryloxypolyethylene glycol with amono-epoxypropyloxypropyl-terminated polydimethylsiloxane, by reactingglycidyl (meth)acrylate with a mono-carbinol-terminatedpolydimethylsiloxane, a mono-aminopropyl-terminatedpolydimethylsiloxane, or a mono-ethylaminopropyl-terminatedpolydimethylsiloxane, ob by reacting isocyanatoethyl (meth)acrylate witha mono-carbinol-terminated polydimethylsiloxane according to couplingreactions well known to a person skilled in the art.

Another class of preferred siloxane containing vinylic monomers isvinylic monomers containing a tris(trimethylsilyloxy)silyl orbis(trimethylsilyloxy)alkylsilyl group (i.e.,tris(trimethylsilyloxy)silyl-containing vinylic monomer orbis(trimethylsilyloxy)alkylsilyl-containing vinylic monomer. Examples ofpreferred siloxane-containing vinylic monomers include withoutlimitation tris(trimethylsilyloxy)silylpropyl (meth)acrylate,[3-(meth)acryloxy-2-hydroxypropyloxy]propylbis(trimethylsiloxy)methylsilane,[3-(meth)acryloxy-2-hydroxypropyloxy]propylbis(trimethylsiloxy)butylsilane,3-(meth)acryloxy-2-(2-hydroxyethoxy)-propyloxy)propylbis(trimethylsiloxy)methylsilane,N-[tris(trimethylsiloxy)silylpropyl]-(meth)acrylamide,N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)-2-methyl(meth)acrylamide,N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)(meth)acrylamide,N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)-2-methylacrylamide,N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)(meth)acrylamide, and mixtures thereof. Preferred siloxane-containingvinylic monomers can be obtained from commercial suppliers or can beprepared according to procedures described in U.S. Pat. Nos. 7,214,809,8,475,529, 8,658,748, 9,097,840, 9,103,965, and 9,475,827.

In accordance with the present invention, the siloxane-containingvinylic monomer is preferably a mono-(meth)acryloyl-terminatedmonoalkyl-terminated polysiloxane, abis(trimethylsilyloxy)alkylsilyl-containing vinylic monomer, or mixturesthereof, more preferably a mono-(meth)acryloyl-terminatedmonoalkyl-terminated polysiloxane having a weight-average molecularweight of about 2500 Daltons or less (preferably about 2000 Daltons orless, more preferably about 1700 Daltons or less, even more preferablyfrom about 450 to about 1500 Daltons).

It is understood that by having at least one H-donor moiety, thesiloxane-containing vinylic monomer can be more compatible withhydrophilic N-vinyl amide monomer compared to one without any H-donormoiety.

In accordance with the invention, any polysiloxane vinylic crosslinkercan be used in the invention, so long as it comprises hydrophilizedsiloxane units each having one methyl substituent and one monovalentC₄-C₄₀ organic radical substituent having one or more H-donor moietiesand has a number average molecular weight of from about 3000 Daltons toabout 80,000 Daltons (preferably from about 4000 to about 40000 Daltons,more preferably from about 5000 to about 20000 Daltons).

Preferably, the first polysiloxane vinylic crosslinker comprises: (1) apolysiloxane segment comprising dimethylsiloxane units and hydrophilizedsiloxane units each having one methyl substituent and one monovalentC₄-C₄₀ organic radical substituent having 2 to 6 second H-donormoieties, wherein the molar ratio of the hydrophilized siloxane units tothe dimethylsiloxane units is from about 0.035 to about 0.15; (2) twoterminal (meth)acryloyl groups; and (3) from 0 to 20 third H-donormoieties, wherein the polysiloxane vinylic crosslinker has a numberaverage molecular weight of from about 3000 Daltons to about 80,000Daltons.

More preferably, the first polysiloxane vinylic crosslinker is acompound of formula (1)

in which:

-   υ1 is an integer of from 30 to 500 and ω1 is an integer of from 1 to    75, provided that ω1/υ1 is from about 0.035 to about 0.15    (preferably from about 0.040 to about 0.12, even more preferably    from about 0.045 to about 0.10);

X₀₁ is O or NR_(n) in which R_(n) is hydrogen or C₁-C₁₀-alkyl;

R₀ is hydrogen or methyl;

R₂ and R₃ independently of each other are a substituted or unsubstitutedC₁-C₁₀ alkylene divalent radical or a divalent radical of —R₅—O—R₆— inwhich R₅ and R₆ independently of each other are a substituted orunsubstituted C₁-C₁₀ alkylene divalent radical;

R₄ is a monovalent radical of any one of formula (2) to (6)

p1 is zero or 1; m1 is an integer of 2 to 4; m2 is an integer of 1 to 5;m3 is an integer of 3 to 6; m4 is an integer of 2 to 5

R₇ is hydrogen or methyl;

R₈ is a C₂-C₆ hydrocarbon radical having (m2+1) valencies;

R₉ is a C₂-C₆ hydrocarbon radical having (m4+1) valencies;

R₁₀ is ethyl or hydroxymethyl;

R₁₁ is methyl or hydromethyl;

R₁₂ is hydroxyl or methoxy;

X₃ is a sulfur linkage of —S— or a tertiary amino linkage of —NR₁₃— inwhich R₁₃ is C₁-C₁ alkyl, hydroxyethyl, hydroxypropyl, or2,3-dihydroxypropyl; and

X₄ is an amide linkage of —NR₁₄—CO— or —CO—NR₁₄— in which R₁₄ ishydrogen or C₁-C₁₀ alkyl.

In a preferred embodiment, the monovalent radical R₄ is a radical offormula (6) in which m1 is 3, p1 is 1, and R₇ is hydrogen. Such apreferred first polysiloxane vinylic crosslinker is represented byformula (A)

in which υ1 and ω1 are as defined above.

The procedures for preparing a polysiloxane vinylic crosslinkers offormula (1) have been described in detail in U.S. Pat. Appl. Pub. No.2017-0166673 A1.

It is understood that component (e) (i.e., at least one secondpolysiloxane vinylic crosslinker) is an optional component in thepolymerizable composition of the invention. Any suitable polysiloxanevinylic crosslinkers other than those polysiloxane vinylic crosslinkershaving hydrophilized siloxane units described above can be used in theinventions, so long as each of them comprises at least one polysiloxanesegment and at least two ethylenically-unsaturated groups. Examples ofsuch polysiloxane vinylic crosslinkers aredi-(meth)acryloyloxy-terminated polydimethylsiloxanes of variousmolecular weight; divinyl carbonate-terminated polydimethylsiloxanes;divinyl carbamate-terminated polydimethylsiloxane; divinyl terminatedpolydimethylsiloxanes of various molecular weight;di-(meth)acrylamido-terminated polydimethylsiloxanes;N,N,N′,N′-tetrakis(3-methacryloxy-2-hydroxypropyl)-alpha,omega-bis-3-aminopropyl-polydimethylsiloxane;chain-extended polysiloxane vinylic crosslinkers which comprises atleast two polysiloxane segments and at least one divalent organicradical linking each pair of adjacent polysiloxane segments and havingone or more H-donor moieties (see, e.g., those disclosed in U.S. Pat.Nos. 5,034,461, 5,416,132, 5,449,729, 5,760,100, 7,423,074, 8,529,057,and 8,993,651 and in U.S. Pat. App. Pub. No. 2018-0100053 A1);siloxane-containing macromer selected from the group consisting ofMacromer A, Macromer B, Macromer C, and Macromer D described in U.S.Pat. No. 5,760,100; the reaction products of glycidyl methacrylate withamino-functional polydimethylsiloxanes; polysiloxane-containingmacromers disclosed in U.S. Pat. Nos. 4,136,250, 4,153,641, 4,182,822,4,189,546, 4,343,927, 4,254,248, 4,355,147, 4,276,402, 4,327,203,4,341,889, 4,486,577, 4,543,398, 4,605,712, 4,661,575, 4,684,538,4,703,097, 4,833,218, 4,837,289, 4,954,586, 4,954,587, 5,010,141,5,034,461, 5,070,170, 5,079,319, 5,039,761, 5,346,946, 5,358,995,5,387,632, 5,416,132, 5,451,617, 5,486,579, 5,962,548, 5,981,675,6,039,913, and 6,762,264; polysiloxane-containing macromers disclosed inU.S. Pat. Nos. 4,259,467, 4,260,725, and 4,261,875.

Examples of preferred di-(meth)acryloyl-terminated polydiorganosiloxanesinclude without limitation α,ω-bis[3-(meth)acrylamidopropyl]-terminatedpolydimethylsiloxane, α,ω-bis[3-(meth)acryloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acryloxy-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acryloxypropyloxy-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acryloxyisopropyloxy-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acryloxybutyloxy-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acrylamidoethoxy-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acrylamidopropyloxy-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acrylamidoisopropyloxy-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acryloxyethylamino-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acryloxypropylamino-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acryloxybutylamino-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[(meth)acrylamidoethylamino-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acrylamidopropylamino-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acrylamide-butylamino-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane, a,ω-bis[(meth)acryloxy-2-hydroxypropyloxy-ethoxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[(meth)acryloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminatedpolydimethylsiloxane,α,ω-bis[(meth)acryloxy-2-hydroxypropyl-aminopropyl]-polydimethylsiloxane,α,ω-bis[(meth)acryloxy-2-hydroxypropyloxy(polyethylenoxy)propyl]-terminatedpolydimethylsiloxane,α,ω-bis[(meth)acryloxyethylaminocarbonyloxy-ethoxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[(meth)acryloxyethylaminocarbonyloxy-(polyethylenoxy)propyl]-terminatedpolydimethylsiloxane.

In accordance with the invention, any suitable N-vinyl amide monomerscan be used in the invention. Examples of preferred N-vinyl amidemonomers include without limitation N-vinyl pyrrolidone, N-vinylpiperidone, N-vinyl caprolactam, N-vinyl-N-methyl acetamide, N-vinylformamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl formamide, andmixtures thereof. Preferably, the N-vinyl amide monomer isN-vinylpyrrolidone, N-vinyl-N-methyl acetamide, or combinations thereof.

In accordance with the invention, a C₁-C₄ alkyl (meth)acrylate is addedin the polymerizable composition in an amount sufficient for increasingthe robusteness of lens shape, preferably in an amount of from about 5to about 30 weight part units, more preferably from about 7 to about 25weight part units or more, even more preferably from about 10 to about20 weight part units relative to the total weight of all polymerizablecomponents in the polymerizable composition. It ie believed that theaddition of a sufficient amount of a C₁-C₄ alkyl (meth)acrylate in apolymerizable composition could increase the rigidity of SiHy contactlenses cast-molded from the polymerizable composition, and therebyincreasing the robusteness of lens shape.

Any suitable thermal polymerization initiators, known to the skilledartisan, can be used in the invention. Examples of thermalpolymerization initiators includes without limitation peroxides,hydroperoxides, azo-bis(alkyl- or cycloalkylnitriles), persulfates,percarbonates or mixtures thereof. Examples of thermal free radicalinitiators are benzoylperoxide, tert.-butyl peroxide,di-tert.-butyl-diperoxyphthalate, tert.-butyl hydroperoxide,azo-bis(isobutyronitrile) (AIBN), 1,1-azodiisobutyramidine, 1,1′-azo-bis(1-cyclohexanecarbonitrile), 2,2′-azo-bis(2,4-dimethylvaleronitrile) andthe like. The polymerization is carried out conveniently in anabove-mentioned solvent at elevated temperature, for example at atemperature of from 25 to 100° C. and preferably 40 to 80° C. Thereaction time may vary within wide limits, but is conveniently, forexample, from 1 to 24 hours or preferably from 2 to 12 hours. It isadvantageous to previously degas the components and solvents used in thepolymerization reaction and to carry out said copolymerization reactionunder an inert atmosphere, e.g., under N₂ or Ar atmosphere.

Suitable photoinitiators are benzoin methyl ether, diethoxyacetophenone,a benzoylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone and Darocurand Irgacur types, preferably Darocur 1173® and Darocur 2959®,Germane-based Norrish Type I photoinitiators. Examples ofbenzoylphosphine initiators include2,4,6-trimethylbenzoyldiphenylophosphine oxide;bis-(2,6-dichlorobenzoyl)-4-N-propylphenylphosphine oxide; andbis-(2,6-dichlorobenzoyl)-4-N-butylphenylphosphine oxide. Reactivephotoinitiators which can be incorporated, for example, into a macromeror can be used as a special monomer are also suitable. Examples ofreactive photoinitiators are those disclosed in EP 632 329. Thepolymerization can then be triggered off by actinic radiation, forexample light, in particular UV light or visible light of a suitablewavelength. The spectral requirements can be controlled accordingly, ifappropriate, by addition of suitable photosensitizers.

Where a vinylic monomer capable of absorbing ultra-violet radiation andhigh energy violet light (HEVL) is used in the invention, aGermane-based Norrish Type I photoinitiator and a light source includinga light in the region of about 400 to about 550 nm are preferably usedto initiate a free-radical polymerization. Any Germane-based NorrishType I photoinitiators can be used in this invention, so long as theyare capable of initiating a free-radical polymerization underirradiation with a light source including a light in the region of about400 to about 550 nm. Examples of Germane-based Norrish Type Iphotoinitiators are acylgermanium compounds described in U.S. Pat. No.7,605,190.

In accordance with the invention, a polymerizable composition canfurther comprise about 1% or less (preferably about 0.8% or less, morepreferably from about 0.05% to about 0.6%) by weight of one or morenon-silicone vinylic crosslinking agents relative to the total weight ofall polymerizable components in the polymerizable composition.

Examples of preferred non-silicone vinylic cross-linking agents includewithout limitation ethyleneglycol di-(meth)acrylate, diethyleneglycoldi-(meth)acrylate, triethyleneglycol di-(meth)acrylate,tetraethyleneglycol di-(meth)acrylate, glycerol di-(meth)acrylate,1,3-propanediol di-(meth)acrylate, 1,3-butanediol di-(meth)acrylate,1,4-butanediol di-(meth)acrylate, glycerol 1,3-diglycerolatedi-(meth)acrylate, ethylenebis[oxy(2-hydroxypropane-1,3-diyl)]di-(meth)acrylate, bis[2-(meth)acryloxyethyl] phosphate,trimethylolpropane di-(meth)acrylate, and3,4-bis[(meth)acryloyl]tetrahydrofuan, diacrylamide (i.e.,N-(1-oxo-2-propenyl)-2-propenamide), dimethacrylamide (i.e.,N-(1-oxo-2-methyl-2-propenyl)-2-methyl-2-propenamide),N,N-di(meth)acryloyl-N-methylamine, N,N-di(meth)acryloyl-N-ethylamine,N,N′-methylene bis(meth)acrylamide, N,N′-ethylene bis(meth)acrylamide,N,N′-dihydroxyethylene bis(meth)acrylamide, N,N′-propylenebis(meth)acrylamide, N,N′-2-hydroxypropylene bis(meth)acrylamide,N,N′-2,3-dihydroxybutylene bis(meth)acrylamide,1,3-bis(meth)acrylamide-propane-2-yl dihydrogen phosphate (i.e.,N,N′-2-phophonyloxypropylene bis(meth)acrylamide), piperazinediacrylamide (or 1,4-bis(meth)acryloyl piperazine), tetraethyleneglycoldivinyl ether, triethyleneglycol divinyl ether, diethyleneglycol divinylether, ethyleneglycol divinyl ether, triallyl isocyanurate, triallylcyanurate, trimethylopropane tri methacrylate, pentaerythritoltetramethacrylate, bisphenol A dimethacrylate, and combinations thereof.A preferred non-silicone vinylic cross-linking agent istetra(ethyleneglycol) di-(meth)acrylate, tri(ethyleneglycol)di-(meth)acrylate, ethyleneglycol di-(meth)acrylate, di(ethyleneglycol)di-(meth)acrylate, tetraethyleneglycol divinyl ether, triethyleneglycoldivinyl ether, diethyleneglycol divinyl ether, ethyleneglycol divinylether, triallyl isocyanurate, or triallyl cyanurate.

In accordance with a preferred embodiment of the invention, apolymerizable composition of the invention can further comprise (butpreferably comprises) one or more UV-absorbing vinylic monomers andoptionally (but preferably) one or more UV/HEVL-absorbing vinylicmonomers. The term “UV/HEVL-absorbing vinylic monomer” refers to avinylic monomer that can absorbs UV light and high-energy-violet-light(i.e., light having wavelength between 380 nm and 440 nm.

Any suitable UV-absorbing vinylic monomers and UV/HEVL-absorbing vinylicmonomers can be used in a polymerizable composition for preparing apolymer of the invention. Examples of preferred UV-absorbing andUV/HEVL-absorbing vinylic monomers include without limitation:2-(2-hydroxy-5-vinylphenyl)-2H-benzotriazole,2-(2-hydroxy-5-acrylyloxyphenyl)-2H-benzotriazole,2-(2-hydroxy-3-methacrylamido methyl-5-tert octylphenyl) benzotriazole,2-(2′-hydroxy-5′-methacrylamidophenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-5′-methacrylamidophenyl)-5-methoxybenzotriazole,2-(2′-hydroxy-5′-methacryloxypropyl-3′-t-butylphenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-5′-methacryloxypropyl phenyl) benzotriazole,2-hydroxy-5-methoxy-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzylmethacrylate (WL-1),2-hydroxy-5-methoxy-3-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)benzylmethacrylate (WL-5),3-(5-fluoro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzylmethacrylate (WL-2),3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzylmethacrylate (WL-3),3-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzylmethacrylate (WL-4),2-hydroxy-5-methoxy-3-(5-methyl-2H-benzo[d][1,2,3]triazol-2-yl)benzylmethacrylate (WL-6),2-hydroxy-5-methyl-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzylmethacrylate (WL-7),4-allyl-2-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-6-methoxyphenol(WL-8),2-{2′-Hydroxy-3′-tert-5-[3″-(4″-vinylbenzyloxy)propoxy]phenyl}-5-methoxy-2H-benzotriazole,phenol,2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-ethenyl-(UVAM),2-[2′-hydroxy-5′-(2-methacryloxyethyl)phenyl)]-2H-benzotriazole(2-Propenoic acid, 2-methyl-,2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl ester, Norbloc),2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-2H-benzotriazole,2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-5-methoxy-2H-benzotriazole(UV13),2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-5-chloro-2H-benzotriazole(UV28),2-[2′-Hydroxy-3′-tert-butyl-5′-(3′-acryloyloxypropoxy)phenyl]-5-trifluoromethyl-2H-benzotriazole(UV23), 2-(2′-hydroxy-5-methacrylamidophenyl)-5-methoxybenzotriazole(UV6), 2-(3-allyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole (UV9),2-(2-Hydroxy-3-methallyl-5-methylphenyl)-2H-benzotriazole (UV12),2-3′-t-butyl-2′-hydroxy-5′-(3″-dimethylvinylsilylpropoxy)-2′-hydroxyphenyl)-5-methoxybenzotriazole(UV15),2-(2′-hydroxy-5′-methacryloylpropyl-3′-tert-butylphenyl)-5-methoxy-2H-benzotriazole(UV16),2-(2′-hydroxy-5′-acryloylpropyl-3′-tert-butylphenyl)-5-methoxy-2H-benzotriazole(UV16A), 2-Methylacrylic acid3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]-propylester (16-100, CAS #96478-15-8),2-(3-(tert-butyl)-4-hydroxy-5-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)phenoxy)ethylmethacrylate (16-102); Phenol,2-(5-chloro-2H-benzotriazol-2-yl)-6-methoxy-4-(2-propen-1-yl) (CAS#1260141-20-5);2-[2-Hydroxy-5-[3-(methacryloyloxy)propyl]-3-tert-butylphenyl]-5-chloro-2H-benzotriazole;Phenol, 2-(5-ethenyl-2H-benzotriazol-2-yl)-4-methyl-, homopolymer (9Cl)(CAS #83063-87-0). In accordance with the invention, the polymerizablecomposition comprises about 0.1% to about 3.0%, preferably about 0.2% toabout 2.5%, more preferably about 0.3% to about 2.0%, by weight of oneor more UV-absorbing vinylic monomers, related to the amount of allpolymerizable components in the polymerizable composition.

In a preferred embodiment, a polymerizable composition of the inventioncomprises a UV-absorbing vinylic monomer and a UV/HEVL absorbing vinylicmonomer. More preferably, the silicone hydrogel contact lens ischaracterized by having the UVB transmittance of about 10% or less(preferably about 5% or less, more preferably about 2.5% or less, evenmore preferably about 1% or less) between 280 and 315 nanometers and aUVA transmittance of about 30% or less (preferably about 20% or less,more preferably about 10% or less, even more preferably about 5% orless) between 315 and 380 nanometers and a Violet transmittance of about70% or less, preferably about 60% or less, more preferably about 50% orless, even more preferably about 40% or less) between 380 nm and 440 nm.Even more preferably, the UV-absorbing vinylic monomer is2-[2′-hydroxy-5′-(2-methacryloxyethyl)phenyl)]-2H-benzotriazole(Norbloc), and the UV/HEVL absorbing vinylic monomer is2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-2H-benzotriazole,2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-5-methoxy-2H-benzotriazole(UV13),2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-5-chloro-2H-benzotriazole(UV28),2-[2′-Hydroxy-3′-tert-butyl-5′-(3′-acryloyloxypropoxy)phenyl]-5-trifluoromethyl-2H-benzotriazole(UV23), or combinations thereof.

In accordance with the invention, a polymerizable composition of theinvention can further comprise one or more hydrophilic acrylic monomers,preferably in an amount of about 10% or less (preferably about 8% orless, more preferably about 5% or less) by weight relative to the totalweight of all polymerizable components.

Examples of preferred hydrophilic acrylic monomers include withoutlimitation N,N-dimethyl (meth)acrylamide, (meth)acrylamide,N-hydroxylethyl (meth)acrylamide, N-hydroxypropyl (meth)acrylamide,hydroxyethyl (meth)acrylate, glycerol methacrylate (GMA), polyethyleneglycol (meth)acrylate having a number average molecular weight of up to1500, polyethylene glycol C₁-C₄-alkyl ether (meth)acrylate having anumber average molecular weight of up to 1500,N-[tris(hydroxymethyl)methyl]-acrylamide, (meth)acrylic acid,ethylacrylic acid, and combinations thereof. Preferably, the hydrophilicvinylic monomer is N,N-dimethyl (meth)acrylamide, hydroxyethyl(meth)acrylate, N-hydroxylethyl (meth)acrylamide, glycerol methacrylate(GMA), or combinations thereof.

A polymerizable composition of the invention can also comprise othernecessary components known to a person skilled in the art, such as, forexample, a visibility tinting agent (e.g., one or more polymerizabledyes, pigments, or mixtures thereof), antimicrobial agents (e.g.,preferably silver nanoparticles), a bioactive agent, leachablelubricants, leachable tear-stabilizing agents, and mixtures thereof, asknown to a person skilled in the art.

In a preferred embodiment, a polymerizable composition of the inventioncomprises about 60% or more by weight (preferably about 65% or more byweight, more preferably about 70% or more by weight, even morepreferably about 75% or more by weight) of all three components,components (a) to (c), relative to the total weight of all polymerizablecomponents.

A polymerizable composition can be prepared by dissolving all of thedesirable components in any suitable solvent, such as, a mixture ofwater and one or more organic solvents miscible with water, an organicsolvent, or a mixture of one or more organic solvents, as known to aperson skilled in the art. The term “solvent” refers to a chemical thatcannot participate in free-radical polymerization reaction.

Example of preferred organic solvents includes without limitation,tetrahydrofuran, tripropylene glycol methyl ether, dipropylene glycolmethyl ether, ethylene glycol n-butyl ether, ketones (e.g., acetone,methyl ethyl ketone, etc.), diethylene glycol n-butyl ether, diethyleneglycol methyl ether, ethylene glycol phenyl ether, propylene glycolmethyl ether, propylene glycol methyl ether acetate, dipropylene glycolmethyl ether acetate, propylene glycol n-propyl ether, dipropyleneglycol n-propyl ether, tripropylene glycol n-butyl ether, propyleneglycol n-butyl ether, dipropylene glycol n-butyl ether, tripropyleneglycol n-butyl ether, propylene glycol phenyl ether dipropylene glycoldimetyl ether, polyethylene glycols, polypropylene glycols, ethylacetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate,i-propyl lactate, methylene chloride, 2-butanol, 1-propanol, 2-propanol,menthol, cyclohexanol, cyclopentanol and exonorborneol, 2-pentanol,3-pentanol, 2-hexanol, 3-hexanol, 3-methyl-2-butanol, 2-heptanol,2-octanol, 2-nonanol, 2-decanol, 3-octanol, norborneol, tert-butanol,tert-amyl alcohol, 2-methyl-2-pentanol, 2,3-dimethyl-2-butanol,3-methyl-3-pentanol, 1-methylcyclohexanol, 2-methyl-2-hexanol,3,7-dimethyl-3-octanol, 1-chloro-2-methyl-2-propanol,2-methyl-2-heptanol, 2-methyl-2-octanol, 2-2-methyl-2-nonanol,2-methyl-2-decanol, 3-methyl-3-hexanol, 3-methyl-3-heptanol,4-methyl-4-heptanol, 3-methyl-3-octanol, 4-methyl-4-octanol,3-methyl-3-nonanol, 4-methyl-4-nonanol, 3-methyl-3-octanol,3-ethyl-3-hexanol, 3-methyl-3-heptanol, 4-ethyl-4-heptanol,4-propyl-4-heptanol, 4-isopropyl-4-heptanol, 2,4-dimethyl-2-pentanol,1-methylcyclopentanol, 1-ethylcyclopentanol, 1-ethylcyclopentanol,3-hydroxy-3-methyl-1-butene, 4-hydroxy-4-methyl-1-cyclopentanol,2-phenyl-2-propanol, 2-methoxy-2-methyl-2-propanol2,3,4-trimethyl-3-pentanol, 3,7-dimethyl-3-octanol, 2-phenyl-2-butanol,2-methyl-1-phenyl-2-propanol and 3-ethyl-3-pentanol,1-ethoxy-2-propanol, 1-methyl-2-propanol, t-amyl alcohol, isopropanol,1-methyl-2-pyrrolidone, N,N-dimethylpropionamide, dimethyl formamide,dimethyl acetamide, dimethyl propionamide, N-methyl pyrrolidinone, andmixtures thereof.

Lens molds for making contact lenses are well known to a person skilledin the art and, for example, are employed in cast molding or spincasting. For example, a mold (for cast molding) generally comprises atleast two mold sections (or portions) or mold halves, i.e. first andsecond mold halves. The first mold half has a first molding (or optical)surface defining the anterior surface of a contact lens and the secondmold half has a second molding (or optical) surface defining theposterior surface of the contact lens. The first and second mold halvesare configured to receive each other such that a lens forming cavity isformed between the first molding surface and the second molding surface.The molding surface of a mold half is the cavity-forming surface of themold and in direct contact with lens-forming material.

Methods of manufacturing mold sections for cast-molding a contact lensare generally well known to those of ordinary skill in the art. Theprocess of the present invention is not limited to any particular methodof forming a mold. In fact, any method of forming a mold can be used inthe present invention. The first and second mold halves can be formedthrough various techniques, such as injection molding or lathing.Examples of suitable processes for forming the mold halves are disclosedin U.S. Pat. Nos. 4,444,711; 4,460,534; 5,843,346; and 5,894,002.

Virtually all materials known in the art for making molds can be used tomake molds for making contact lenses. For example, polymeric materials,such as polyethylene, polypropylene, polystyrene, PMMA, Topas® COC grade8007-S10 (clear amorphous copolymer of ethylene and norbornene, fromTicona GmbH of Frankfurt, Germany and Summit, N.J.), or the like can beused. Other materials that allow UV light transmission could be used,such as quartz glass and sapphire.

In accordance with the invention, the polymerizable composition can beintroduced (dispensed) into a cavity formed by a mold according to anyknown methods.

After the polymerizable composition is dispensed into the mold, it ispolymerized to produce a contact lens. Crosslinking may be initiatedthermally or actinically to crosslink the polymerizable components inthe polymerizable composition.

Opening of the mold so that the molded article can be removed from themold may take place in a manner known per se.

The molded contact lens can be subject to lens extraction to removeunpolymerized polymerizable components. The extraction solvent can beany solvent known to a person skilled in the art. Examples of suitableextraction solvent are those solvent described above. After extraction,lenses can be hydrated in water or an aqueous solution of a wettingagent (e.g., a hydrophilic polymer).

The molded contact lenses can further subject to further processes, suchas, for example, hydration, packaging in lens packages with a packagingsolution which is well known to a person skilled in the art;sterilization such as autoclave at from 118 to 124° C. for at leastabout 30 minutes; and the like.

Lens packages (or containers) are well known to a person skilled in theart for autoclaving and storing a soft contact lens. Any lens packagescan be used in the invention. Preferably, a lens package is a blisterpackage which comprises a base and a cover, wherein the cover isdetachably sealed to the base, wherein the base includes a cavity forreceiving a sterile packaging solution and the contact lens.

Lenses are packaged in individual packages, sealed, and sterilized(e.g., by autoclave at about 120° C. or higher for at least 30 minutesunder pressure) prior to dispensing to users. A person skilled in theart will understand well how to seal and sterilize lens packages.

Although various embodiments of the invention have been described usingspecific terms, devices, and methods, such description is forillustrative purposes only. The words used are words of descriptionrather than of limitation. It is to be understood that changes andvariations may be made by those skilled in the art without departingfrom the spirit or scope of the present invention, which is set forth inthe following claims. In addition, it should be understood that aspectsof the various embodiments may be interchanged either in whole or inpart or can be combined in any manner and/or used together.

The previous disclosure will enable one having ordinary skill in the artto practice the invention. Various modifications, variations, andcombinations can be made to the various embodiment described herein. Inorder to better enable the reader to understand specific embodiments andthe advantages thereof, reference to the following examples issuggested. It is intended that the specification and examples beconsidered as exemplary.

Example 1 Oxygen Permeability Measurements

Unless specified, the apparent oxygen permeability (Dk_(app)), theapparent oxygen transmissibility (Dk/t), the intrinsic (oredge-corrected) oxygen permeability (Dk_(i) or Dk_(c)) of a lens and alens material are determined according to procedures described inExample 1 of U.S. Pat. Appl. Pub. No. 2012-0026457 A1.

Surface Wettability Tests

Water contact angle (WCA) on a contact lens is a general measure of thesurface wettability of a contact lens. In particular, a low watercontact angle corresponds to more wettable surface. The dynamic captivebubble contact angles of contact lenses are measured using a FDSinstrument device from FDS Future Digital Scientific Corp. The FDSequipment is capable of measuring the advancing and receding contactangles. The measurement is performed on hydrated contact lenses at roomtemperature. A contact lens is removed from the vial and soaked in ˜40mL fresh phosphate buffered saline (PBS) and shake for at least 30minutes, then replace with fresh PBS, soak and shake for another 30minutes unless otherwise specified. The contact lens is then put on alens paper and dabbed to remove surface water prior to be placed on topof a lens holder with front curve up then screw the lens holder top on.Place the secure lens holder into the glass cell cuvette filled withfiltered PBS. Place the glass cell cuvette onto the stage of the FDSinstrument. Adjust the stage height and the syringe needle to dispensethe air bubble to the lens surface. Repeat dispense/withdraw) 3 cyclesfor every lens to get the advancing and receding contact angles. Thereceding contact angles are reported in the examples below.

Water Break-Up Time (WBUT) Tests

The surface hydrophilicity of lenses (after autoclave) is assessed bydetermining the time required for the water film to start breaking onthe lens surface. Lenses exhibiting WBUT 10 seconds are considered tohave a hydrophilic surface and are expected to exhibit adequatewettability (ability to support the tear film) on-eye.

Lenses are prepared for water breakup measurement by removing the lensfrom its blister with soft plastic tweezers (Menicon) and placing thelens in a beaker containing phosphate buffered saline. The beakercontains at least 20 mL phosphate buffered saline per lens, with up to 3lenses per beaker. Lenses are soaked for a minimum 30 minutes up to 24hours before being transferred with soft plastic tweezers into a 96 wellplastic tray with fresh phosphate buffered saline.

Water breakup time is measured at room temperature as follows: lensesare picked up with soft plastic tweezers as close to the edge of thelens as possible, base curve toward the measurer, taking care that thelens does not touch the sides of the well after being removed from thesaline. As illustrated schematically in FIG. 1, the lens (101) is shakenonce to remove excess saline and a timer is started. Ideally, the waterfilm (120) in the base curve surface of the lens will recede from thepoint of contact with the tweezers's tips (111) in a uniform, circularpattern (125). When approximately 30% of the hydrated area (125) hasreceded, the timer is stopped and this time is recorded as the waterbreakup time (WBUT). Lenses that do not display the ideal recedingpattern can be placed back in the tray and re-measured, afterrehydrating for at least 30 seconds.

Equilibrium Water Content

The equilibrium water content (EWC) of contact lenses are determined asfollows.

Amount of water (expressed as percent by weight) present in a hydratedhydrogel contact lens, which is fully equilibrated in saline solution,is determined at room temperature. Quickly stack the lenses, andtransfer the lens stack to the aluminum pan on the analytical balanceafter blotting lens in a cloth. The number of lenses for each sample panis typically five (5). Record the pan plus hydrated weight of thelenses. Cover the pan with aluminum foil. Place pans in a laboratoryoven at 100±2° C. to dry for 16-18 hours. Remove pan plus lenses fromthe oven and cool in a desiccator for at least 30 minutes. Remove asingle pan from the desiccator, and discard the aluminum foil. Weigh thepan plus dried lens sample on an analytical balance. Repeat for allpans. The wet and dry weight of the lens samples can be calculated bysubtracting the weight of the empty weigh pan.

Elastic Modulus

The elastic modulus of a contact lens is determined using a MTS insightinstrument. The contact lens is first cut into a 3.12 mm wide stripusing Precision Concept two stage cutter. Five thickness values aremeasured within 6.5 mm gauge length. The strip is mounted on theinstrument grips and submerged in PBS (phosphate buffered saline) withthe temperature controlled at 21±2° C. Typically 5N Load cell is usedfor the test. Constant force and speed is applied to the sample untilthe sample breaks. Force and displacement data are collected by theTestWorks software. The elastic modulus value is calculated by theTestWorks software which is the slope or tangent of the stress vs.strain curve near zero elongation, in the elastic deformation region.

Transmittance

Contact lenses are manually placed into a specially fabricated sampleholder or the like which can maintain the shape of the lens as it wouldbe when placing onto eye. This holder is then submerged into a 1 cmpath-length quartz cell containing phosphate buffered saline (PBS,pH˜7.0-7.4) as the reference. A UV/visible spectrpohotmeter, such as,Varian Cary 3E UV-Visible Spectrophotometer with a LabSphere DRA-CA-302beam splitter or the like, can be used in this measurement. Percenttransmission spectra are collected at a wavelength range of 250-800 nmwith % T values collected at 0.5 nm intervals. This data is transposedonto an Excel spreadsheet and used to determine if the lenses conform toClass 1 UV absorbance. Transmittance is calculated using the followingequations:

${{UVA}\mspace{14mu} \% \mspace{14mu} T} = {\frac{{{Average}\mspace{14mu} \% \mspace{14mu} T\mspace{14mu} {between}\mspace{14mu} 380\text{-}316\mspace{14mu} {nm}}\;}{{Luminescence}\mspace{14mu} \% \mspace{14mu} T} \times 100}$${{UVB}\mspace{14mu} \% \mspace{14mu} T} = {\frac{{Average}\mspace{14mu} \% \mspace{14mu} T\mspace{14mu} {between}\mspace{14mu} 280\text{-}315\mspace{14mu} {nm}}{{Luminescence}\mspace{14mu} \% \mspace{14mu} T} \times 100}$${{Violet}\mspace{14mu} \% \mspace{14mu} T} = {\frac{{Average}\mspace{14mu} \% \mspace{14mu} T\mspace{14mu} {between}\mspace{14mu} 440\text{-}380\mspace{14mu} {nm}}{{Luminescence}\mspace{14mu} \% \mspace{14mu} T} \times 100}$

in which Luminescence % T is the average % transmission between 380 and780.

Chemicals

The following abbreviations are used in the following examples: NVPrepresents N-vinylpyrrolidone; DMA represents N,N-dimethylacrylamide;VMA represents N-vinyl-N-methyl acetamide; MMA represents methylmethacrylate; TEGDMA represent triethyleneglycol dimethacrylate; TEGDVErepresents triethyleneglycol divinyl ether; EGMA represents ethyleneglycol methyl ether methacrylate; VAZO 64 represents2,2′-dimethyl-2,2′azodipropiononitrile; Nobloc is2-[3-(2H-Benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate fromAldrich; UV28 represents2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-5-chloro-2H-benzotriazole;RB246 is Reactive Blue 246; RB247 is Reactive Blue 247; TAA representstert-amyl alcohol; PrOH represents n-propanol; IPA representsisopropanol; DC 1173 represents Darocur 1173® photoinitiator; MeCNrepresents acetonitrile; SiGMA represents3-(3-methacryloxy-2-hydroxypropyloxypropyl-bis(trimethylsiloxy)methylsilane;mSi1 represents monobutyl-terminated monomethacryloxypropyl-terminatedpolydimethylsiloxane (Mw˜600 to 800 g/mol from Gelest); mSi2 representsmonobutyl-terminated monomethacryloxypropyl-terminatedpolydimethylsiloxane (Mw˜1100 g/mol from Gelest); D3 representsmonobutyl-terminated monomethacryloxypropyl-terminatedpolydimethylsiloxane (Mw˜539 g/mol from Shin-Etsu); D6 representsmonobutyl-terminated monomethacryloxypropyl-terminatedpolydimethylsiloxane (Mw˜761 g/mol from Shin-Etsu); D9 representsmonobutyl-terminated monomethacryloxypropyl-terminatedpolydimethylsiloxane (Mw˜984 g/mol from Shin-Etsu); D7 representsmonobutyl-terminated monomethacryloxypropyl-terminatedpolydimethylsiloxane (Mw˜750 g/mol from Shin-Etsu); D8 representsmonobutyl-terminated monomethacryloxypropyl-terminatedpolydimethylsiloxane (Mw˜850 g/mol from Shin-Etsu); LM-CEPDMS representsa di-methacrylate-terminated chain-extended polydimethylsiloxane(Mn˜6000 g/mol), which has three polydimethylsiloxane (PDMS) segmentslinked via diurethane linkages between two PDMS segments and twourethane linkages each located between one terminal methacrylate groupand one PDMS segment, is prepared according to method similar to whatdescribed in Example 2 of U.S. Pat. No. 8,529,057; CEPDMS represents adi-methacrylate-terminated chain-extended polydimethylsiloxane (Mn˜9000g/mol), which has three polydimethylsiloxane (PDMS) segments linked viadiurethane linkages between two PDMS segments and two urethane linkageseach located between one terminal methacrylate group and one PDMSsegment, is prepared according to method similar to what described inExample 2 of U.S. Pat. No. 8,529,057; Betacon represents adimethacrylate-terminated chain-extended polydimethylsiloxane (Mn˜5000g/mol), which has two polydimethylsiloxane (PDMS) segments separated byone perfluoropolyether (PFPE) via diurethane linkages between PDMS andPFPE segments and two urethane linkages each located between oneterminal methacrylate group and one PDMS segment, is prepared accordingto method similar to what described in Example B-1 of U.S. Pat. No.5,760,100; “GA” macromer represents adi-methacryloyloxypropyl-terminated polysiloxane (Mn˜6.8K g/mol, OHcontent˜1.2 meq/g) of formula (A) shown above; “G0” macromer representsa di-methacryloyloxypropyl-terminated polysiloxane (Mn˜8.0K g/mol, OHcontent˜1.8 meq/g) of formula (A) shown above; “G1” macromer representsa di-methacryloyloxypropyl-terminated polysiloxane (Mn˜10.7K g/mol, OHcontent˜1.8 meq/g) of formula (A) shown above; “G3” macromer representsa di-methacryloyloxypropyl-terminated polysiloxane (Mn˜16.3K g/mol, OHcontent˜1.8 meq/g) of formula (A) shown above; “G4” macromer representsa di-methacryloyloxypropyl-terminated polysiloxane (Mn˜13.5K g/mol, OHcontent 1.8 meq/g) of formula (A) shown above; “G5” macromer representsa di-methacryloyloxypropyl-terminated polysiloxane (Mn˜14.8K g/mol, OHcontent˜2.2 meq/g) of formula (A) shown above; “G6” macromer representsa di-methacryloyloxypropyl-terminated polysiloxane (Mn˜17.9K g/mol, OHcontent˜2.2 meq/g) of formula (A) shown above. All thedi-methacryloyloxypropyl-terminated polysiloxane of formula (A) areprepared according to the procedures described in U.S. Pat. Appl. Pub.No. 2017-0166673 A1.

Example 2

A lens formulation is purged with nitrogen at room temperature for 30 to35 minutes. The N₂-purged lens formulation is introduced intopolypropylene molds and thermally cured in an oven under the followingcuring conditions: ramping from room temperature to a first temperatureand then holding at the first temperature for a first curing timeperiod; ramping from the first temperature to a second temperature andholding at the second temperature for a second curing time period;optionally ramping from the second temperature to a third temperatureand holding at the third temperature for a third curing time period; andoptionally ramping from the third temperature to a fourth temperatureand holding at the fourth temperature for a fourth curing time period.

Lens molds are opened by using a demolding machine with a push pin.Lenses are pushed onto base curve molds with a push pin and then moldsare separated into base curve mold halves and front curve mold halves.The base curve mold halves with a lens thereon are placed in anultrasonic device (e.g., Dukane's single horn ultrasonic device). With acertain energe force, a dry state lens is released from mold. The drystate lens is loaded in a designed extraction tray. Alternatively,lenses can be removed from the base curve mold halves by floating off(i.e., soaking in an organic solvent (e.g., IPA) without ultrasonic. Thelenses removed from the molds are subjected to an extraction processusing water or an organic solvent or a mixture of solvents for at least30 minutes. For example, extracted in 50% IPA for 30 min, or in 100% IPAfor 15 min then back to 50% IPA for 30 min, DI water for 30 min andfinally in PBS saline overnight. Inspected lens is packaged in lenspackages containing a phosphate buffered saline (pH˜7.2) and autoclavedat 121° C. for about 30-45 minutes.

Example 3

A lens formulation is purged with nitrogen at room temperature for 30 to35 minutes. The N₂-purged lens formulation is introduced intopolypropylene molds and cured by UV/visible light (Hamamatsu lamp) for acuring time period. The post cast molding procedures described inExample 2 are used in this process for producing SiHy contact lenses.

Examples 4-24

In Examples 4 to 24, polymerizable compositions are prepared and listedin Tables 1-4. All the concentrations of the components listed in thetables are weight part units. The prepared polymerizable compositionscomprises 0.01 weight part of a reactive dye (RB246 or RB247) and 0.5weight part of free radical initiator (either VAZO 64 for thermallycurable compositions or DC1173 for UV-curable compositions).

TABLE 1 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 1^(st) mPDMS 40 (mSi1) 33(mSi1) 33 (mSi2) 30 (mSi1) 26 (mSi1) 40 (mSi2) Si Macromer 5 (CE-PDMS)10 (CE-PDMS) 10 (CE-PDMS) 14 (CE-PDMS) 17 (CE-PDMS) 5 (CE-PDMS) NVP 4340 40 44 43 43 MMA 10 15 15 10 15 10 TEGDMA 0.2 0.2 0.2 0.2 0.2 0.2Solvent 0 0 0 6 (TAA) 0 0 Curing Profile 55/70/100° C. 55/70/100° C.55/70/100° C. 55/70/100° C. 55/70/100° C. 55/70/100° C. 4 h/4 h/1 h 4h/4 h/1 h 4 h/4 h/1 h 4 h/4 h/1 h 4 h, 4 h, 1 h 4 h/4 h/1 h ExtractionMedium IPA IPA IPA IPA IPA IPA

TABLE 2 Ex. 10 Ex. 11 Ex. 12 Ex. 13* Ex. 14 Ex. 15 1^(st) mPDMS 26(mSi2) 35 (mSi1) 37 (mSi2) 18 (mSi2) 34 (D6) 22 (D3) 2^(nd) mPDMS 0 0 016 (mSi1) 0 0 Si Macromer 17 (CE-PDMS) 5 (CE-PDMS) 3 (betacon) 5(betacon) 6 (GA) 25 (G1) NVP 40 48 50 50 40 43 MMA 15 10 10 5 10 10TEGDMA 0.2 0.2 0.5 1 0.2 0.2 HEMA 0 0 0 0 0.2 0 TEGDVE 0 0 0.1 0.1 0 0Norbloc 0.9 0.9 0.9 0.9 0.9 2 Solvent 10 (1-hexanol) 10 (1-PrOH) 0 0 3(TAA) 0 Curing Profile 55/70/100° C. 55/70/100° C. 55/80/100° C.55/80/100° C. 55/80/100° C.; 55/80/100° C. 4 hr/4 hr/1 hr 4 hr/4 hr/1 hr(40 min/)₂40 min (40 min/)₂40 min (30 min/)₂30 min 1 hr/1 hr/1 hrExtraction medium IPA IPA IPA; & aqueous IPA, & aqueous H2O; & IPA IPA*also contains 5 weight part units of methoxy ethyleneglycolmethacrylate.

TABLE 3 Ex. 16 Ex. 17 Ex. 18 Ex. 19 Ex. 20 Ex. 21 1st mPDMS 25 (D3) 35(D3) 33 (mSi1) 25 (mSi1) 30 (D9) 35 (D6) Si Macromer 25 (G1) 10 (G1) 4(LMW-CEPDMS) 25 (GA) 16 (G3) 12 (G1) NVP 40 48 53 40 45 46 MMA 10 7 1010 7 7 TEGDMA 0.2 0.2 0.2 0.2 0.2 0.2 Norbloc 2 2 2 2 2 2 Solvent 0 0 00 7 (TAA) 3 (TAA) Curing Profile 55/80/100° C. 55/80/100° C. 55/80/100°C. 55/80/100° C. 55/80/100° C. 55/80/100° C. 1 hr/1 hr/1 hr 1 hr/1 hr/1hr 1 hr/1 hr/1 hr 1 hr/1 hr/1 hr 1 hr/1 hr/1 hr 1 hr/1 hr/1 hrExtraction IPA IPA H₂O IPA IPA IPA medium

TABLE 4 Ex. 22 Ex. 23 Ex. 24 1st mPDMS 18 (mSi2) 18 (mSi2) 36.5 (D3) 2ndmPDMS 16 (mSi1) 16 (mSi1) 0 Si Macromer 5 (betacon) 5 (LMW-CEPDMS) 7.7(CE-PDMS) NVP 50 50 43.8 MMA 5 5 10 TEGDMA 1 1 0 DMA 0.1 0.1 0 Initiator0.5 (DC1173) 0.5 (DC1173) 0.5 (VAZO 64) Curing 5 mW/cm² 5 mW/cm² 30 min55/70/100° C. Profile 30 min 4 hr/4 hr/1 hr Extraction IPA; & aqueousIPA; & aqueous IPA medium

SiHy contact lenses are prepared from those polymerizable compositionsaccording to curing processes described in Example 2 or 3. The lensproperties of resultant SiHy contact lenses are determined according toprocedure described in Example 1 and reported in Table 5.

TABLE 5$\frac{\lbrack{NVA}\rbrack \mspace{14mu} {mmol}}{\left\lbrack {{Si}\mspace{14mu} {comp}} \right\rbrack \mspace{14mu} g}$$\frac{\left\lbrack {H\text{-}D} \right\rbrack \mspace{14mu} {meq}}{\lbrack{NVA}\rbrack \mspace{14mu} g}$Dk (Barrers) EWC (%) Modulus (MPa) WBUT (s) WCA_(CB) (°) Ex. 4 8.6 0.078NA NA NA 2 NA Ex. 5 8.4 0.17 NA NA NA 1 NA Ex. 6 8.4 0.17 NA NA NA 1 NAEx. 7 9.0 0.21 106 NA 0.79 10 NA Ex. 8 9.0 0.26 NA NA NA 5 NA Ex. 9 8.60.078 NA NA NA 5 NA Ex. 10 8.4 0.28 NA NA NA 5 NA Ex. 11 10.8 0.07 NA NANA <1  NA Ex. 12 11.2 0.072 NA 50.8 1.11 3~5 NA Ex. 13 11.5 0.10 NA NANA 0~2 NA Ex. 14 9.0 0.18 85 49 0.69 15 NA Ex. 15 8.2 1.05 106 44 NA <5 NA Ex. 16 7.2 1.13 120 41 NA <1  NA Ex. 17 9.6 0.38 113 48 0.77 10 54Ex. 18 12.9 0.075 88 0.6 5 55 Ex. 19 7.2 0.75 117 40 1.2 8 NA Ex. 20 8.80.64 126 54 0.66 30 44 Ex. 21 8.8 0.47 112 52 0.65 14 45 Ex. 22 11.50.12 NA NA 0.44 15 25~40 Ex. 23 11.5 0.10 NA NA NA 15 40 Ex. 24 8.9 0.1285 50 0.56 11 64 NVA: N-vinyl amide monomer(s); H-D: H-donor moieties;Si-comp: all silicone-containing polymerizable component.

As shown in Table 5, there are two limitations on the amounts of thesiloxane-containing vinylic monomer, the linear polysiloxane vinyliccrosslinker and the N-vinyl amide monomer in a polymerizable compositionfor forming inherently wettable SiHy contact lenses.

The first limitation appears to be that there is a threshold amount ofthe N-vinyl amide monomer relative to the total amount of allsilicone-containing polymerizable components. That threshold value ofthe amount of the N-vinyl amide monomer is likely around 8.8 mmoles pergram of all the silicone-containing polymerizable components. In orderto form inherently wettable SiHy contact lenses, a polymerizablecomposition should comprise about 8.8 mmoles or more per gram of allsilicone-containing polymerizable components present in thepolymerizable composition.

The second limitation appears to be that there is also a threshold valuefor the total amount of the H-donor moieties (“H-D”) contributed by thepolysiloxane vinylic crosslinker and the siloxane-containing vinylicmonomer relative to the amount of the N-vinyl amide monomer. Thatthreshold value appears to be around 0.11 meqs of H-donor moieties pergram of the N-vinyl amide monomer. In order to form inherently wettableSiHy contact lenses, a polymerizable composition should comprise about0.11 meqs or more of H-donor moieties (contributed from all thesilicone-containing polymerizable components) per gram of the N-vinylamide monomer.

Examples 25-28

In Examples 25 to 28, polymerizable compositions are prepared and listedin Table 6. All the concentrations of the components listed in thetables are weight part units. SiHy contact lenses are prepared fromthose polymerizable compositions according to curing processes describedin Example 2 or 3. The lens properties of resultant SiHy contact lensesare determined according to procedure described in Example 1 andreported also in Table 6.

TABLE 6 Ex. 25 Ex. 26 Ex. 27 Ex. 28 MCR-MO7 35 (mSi1) 35 (mSi1) 35(mSi1) 35 (mSi1) H1 10 (G1) 10 (G1) 10 (G1) 10 (G1) NVP 48  48 48 48 MMA0 3 7 7 TEGDMA   0.1 0.1 0.1 0.1 Norbloc   1.8 1.8 1.8 1.8 Vazo64   0.50.5 0.5 0.5 RB247   0.01 0.01 0.01 0.01 T-Amyl Alcohol 7 10 0 10 CuringProfile 55/80/100° C., 55/80/100° C., 55/80/100° C., 55/80/100° C., 1hr/1 hr/1 hr 1 hr/1 hr/1 hr 1 hr/1 hr/1 hr 1 hr/1 hr/1 hr Extraction IPAIPA IPA IPA$\frac{\lbrack{NVA}\rbrack \mspace{14mu} {mmol}}{\left\lbrack {{Si}\mspace{14mu} {comp}} \right\rbrack \mspace{14mu} g}$ 12.3 12.3 12.3 12.3$\frac{\left\lbrack {H\text{-}D} \right\rbrack \mspace{14mu} {meq}}{\lbrack{NVA}\rbrack \mspace{14mu} g}$  0.38 0.38 0.38 0.38 Lens shape Hazy, Hazy, Round lens shape Round lensshape Wrinkled surface, Wrinkled surface, non-round lens non-round lensshape shape Dk (barrers) 126*  NA 109 102 EWC (%) 48* NA 50 50 Modulus(MPa)    0.77* NA 0.73 0.64 WBUT (s) NA NA 20 23 WCA_(CB) (°) NA NA 4542 *only for reference due to defects in lens morphology.

SiHy lenses of Example 13 have a round lens shape. The results ofExample 13 and those in Table 6 shows that when a polymerizablecomposition comprises at least 5 weight part units of methylmethacrylate, the resultant SiHy lenses prepared from such a compositionare inherently wettable and have a robusteness of lens shape.

All the publications, patents, and patent application publications,which have been cited herein above in this application, are herebyincorporated by reference in their entireties.

What is claimed is:
 1. A method for producing inherently-wettablesilicone hydrogel contact lenses, comprising the steps of: (1) preparinga polymerizable composition which is clear at room temperature, whereinthe polymerizable composition comprises (a) at least onesiloxane-containing vinylic monomer including 0 to 10 first H-donormoieties, (b) at least one first polysiloxane vinylic crosslinker whichhas a number average molecular weight of from about 3000 Daltons toabout 80,000 Daltons and comprises (i) two terminal (meth)acryloylgroups, (ii) at least one polysiloxane segment comprisingdimethylsiloxane units and hydrophilized siloxane units each having onemethyl substituent and one monovalent C₄-C₄₀ organic radical substituenthaving one or more second H-donor moieties, and (iii) from 0 to 20 thirdH-donor moieties which are integral parts of molecular structuresoutside of the polysiloxane segment, (c) at least one hydrophilicN-vinyl amide monomer, (d) a C₁-C₄ alkyl (meth)acrylate in an amount forincreasing the robusteness of lens shape of silicone hydrogel contactlenses produced from the polymerizable composition relative to a controlpolymerizable composition free of C₁-C₄ alkyl (meth)acrylate, and (e)optionally at least one second polysiloxane vinylic crosslinker having 0to 35 fourth H-donor moieties, and (f) at least one free radicalinitiator, wherein the first and second polysiloxane vinylic crosslinkerare different from each other, wherein the first, second, third andfourth H-donor moieties independent of one another are hydroxyl groups,carboxyl groups, amino groups of —NHR^(o), amino linkages of —NH—, amidelinkages of —CONH—, urethane linkages of —OCONH—, or combinationsthereof, wherein R^(o) is H or a C₁-C₄ alkyl, wherein the polymerizablecomposition comprises at least 8.8 mmoles of component (c) per gram ofall components (a), (b) and (e) in total and at least 0.11 meqs of allthe first, second, third and fourth H-donor moieties in total per gramof component (c); (2) introducing the polymerizable composition into amold; and (3) curing thermally or actinically the polymerizablecomposition in the lens mold to form a silicone hydrogel contact lens,wherein the silicone hydrogel contact lens has an oxygen permeability ofat least 50 barrers, an elastic modulus of from about 0.2 MPa to about1.5 MPa, and an equilibrium water content of from about 40% to about 70%by weight and is inherently wettable as characterized by having awater-break-up-time of at least 10 seconds and a water contact angle bycaptive bubble of about 80 degrees or less without being subjected toany post-curing surface treatment.
 2. The method of claim 1, wherein thepolymerizable composition comprises at least 5 weight part units of aC₁-C₄ alkyl (meth)acrylate relative to the total weight of allpolymerizable components in the polymerizable composition.
 3. The methodof claim 2, wherein hydrophilized siloxane units each have one methylsubstituent and one monovalent C₄-C₄₀ organic radical substituent having2 to 6 second H-donor moieties.
 4. The method of claim 3, wherein thefirst polysiloxane vinylic crosslinker is a compound of formula (1)

in which: υ1 is an integer of from 30 to 500 and ω1 is an integer offrom 1 to 75, provided that ω1/υ1 is from about 0.035 to about 0.15; X₀₁is O or NR_(n) in which R_(n) is hydrogen or C₁-C₁₀-alkyl; R_(o) ishydrogen or methyl; R₂ and R₃ independently of each other are asubstituted or unsubstituted C₁-C₁₀ alkylene divalent radical or adivalent radical of —R₅—O—R₆— in which R₅ and R₆ independently of eachother are a substituted or unsubstituted C₁-C₁₀ alkylene divalentradical; R₄ is a monovalent radical of any one of formula (2) to (6)

p1 is zero or 1; m1 is an integer of 2 to 4; m2 is an integer of 1 to 5;m3 is an integer of 3 to 6; m4 is an integer of 2 to 5; R₇ is hydrogenor methyl; R₈ is a C₂-C₆ hydrocarbon radical having (m2+1) valencies; R₉is a C₂-C₆ hydrocarbon radical having (m4+1) valencies; R₁₀ is ethyl orhydroxymethyl; R₁₁ is methyl or hydromethyl; R₁₂ is hydroxyl or methoxy;X₃ is a sulfur linkage of —S— or a tertiary amino linkage of —NR₁₃— inwhich R₁₃ is C₁-C₁ alkyl, hydroxyethyl, hydroxypropyl, or2,3-dihydroxypropyl; and X₄ is an amide linkage of

in which R₁₄ is hydrogen or C₁-C₁₀ alkyl.
 5. The method of claim 4,wherein R₄ is a radical of formula (6) in which m1 is 3 and p1 is
 1. 6.The method of claim 4, the siloxane-containing vinylic monomer is amono-(meth)acryloyl-terminated monoalkyl-terminated polysiloxane havinga weight average molecular weight of about 2500 Daltons or less.
 7. Themethod of claim 6, wherein the mono-(meth)acryloyl-terminated,monoalkyl-terminated polysiloxane is α-(meth)acryloxypropyl terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-(meth)acryloxy-2-hydroxypropyloxypropyl terminated ω-butyl (orω-methyl) terminated polydimethylsiloxane,α-(2-hydroxyl-methacryloxypropyloxypropyl)-ω-butyl-decamethylpentasiloxane,α-[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl]-terminated ω-butyl(or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloxypropyloxy-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloxyisopropyloxy-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloxybutyloxy-2-hydroxypropyloxypropyl]-terminated ω-butyl(or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloxyethylamino-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloxypropylamino-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloxybutylamino-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-(meth)acryloxy(polyethylenoxy)-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[(meth)acryloxy-2-hydroxypropyloxy-ethoxypropyl]-terminated ω-butyl(or ω-methyl) terminated polydimethylsiloxane,α-[(meth)acryloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated ω-butyl(or ω-methyl) terminated polydimethylsiloxane,α-[(meth)acryloxy-2-hydroxypropyl-aminopropyl]-terminated ω-butyl (orω-methyl) terminated polydimethylsiloxane,α-[(meth)acryloxy-2-hydroxpropyloxy(polyethylenoxy)propyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-(meth)acryloylamidopropyloxypropyl terminated ω-butyl (or ω-methyl)terminated polydimethylsiloxane,α-N-methyl-(meth)acryloylamidopropyloxypropyl terminated ω-butyl (orω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acrylamidoethoxy-2-hydroxypropyloxypropyl]-terminated ω-butyl(or ω-methyl) polydimethylsiloxane,α-[3-(meth)acrylamidopropyloxy-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acrylamidoisopropyloxy-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloylamido-2-hydroxypropyloxypropyl] terminated ω-butyl(or ω-methyl) polydimethylsiloxane,α-[3-[N-methyl-(meth)acryloylamido]-2-hydroxypropyloxypropyl] terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,N-methyl-N′-(propyltetra(dimethylsiloxy)dimethylbutylsilane)(meth)acrylamide,N-(2,3-dihydroxypropane)-N′-(propyltetra(dimethylsiloxy)dimethylbutylsilane)(meth)acrylamide,(meth)acryloylamidopropyltetra(dimethylsiloxy)dimethylbutylsilane, or amixture thereof.
 8. The method of claim 4, wherein the siloxanecontaining vinylic monomers is a vinylic monomer containing atris(trimethylsilyloxy)silyl or bis(trimethylsilyloxy)alkylsilyl group.9. The method of claim 8, wherein thetris(trimethylsilyloxy)silyl-containing orbis(trimethylsilyloxy)alkylsilyl-containing vinylic monomer is selectedfrom the group consisting of tris(trimethylsilyloxy)silylpropyl(meth)acrylate,[3-(meth)acryloxy-2-hydroxypropyloxy]propylbis(trimethylsiloxy)methylsilane,[3-(meth)acryloxy-2-hydroxypropyloxy]propylbis(trimethylsiloxy)butylsilane,3-(meth)acryloxy-2-(2-hydroxyethoxy)-propyloxy)propylbis(trimethylsiloxy)methylsilane,N-[tris(trimethylsiloxy)silylpropyl]-(meth)acrylamide,N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)-2-methyl(meth)acrylamide,N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)(meth)acrylamide,N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)-2-methylacrylamide,N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)(meth)acrylamide, and mixtures thereof.
 10. The method of claim 6,wherein the hydrophilic N-vinyl amide monomer is N-vinylpyrrolidone,N-vinyl piperidone, N-vinyl caprolactam, N-vinyl-N-methyl acetamide,N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide,N-vinyl-N-methyl acetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethylformamide, and mixtures thereof.
 11. The method of claim 10, wherein thepolymerizable composition further comprises one or more non-siliconevinylic crosslinking agents.
 12. The method of claim 11, wherein thepolymerizable composition further comprises at least one UV-absorbingvinylic monomer and optionally at least one UV/HEVL-absorbing vinylicmonomer.
 13. The method of claim 12, wherein the polymerizablecomposition further comprises2-[2′-hydroxy-5′-(2-methacryloxyethyl)phenyl)]-2H-benzotriazole(Norbloc) and at least one UV/HEVL-absorbing vinylic monomer selectedfrom the group consisting of2-{2′-Hydroxy-3′-tert-butyl-5-[3′-methacryloyloxypropoxy]phenyl}-2H-benzotriazole,2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-5-methoxy-2H-benzotriazole(UV13),2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-5-chloro-2H-benzotriazole(UV28),2-[2′-Hydroxy-3′-tert-butyl-5′-(3′-acryloyloxypropoxy)phenyl]-5-trifluoromethyl-2H-benzotriazole(UV23), and combinations thereof.
 14. The method of claim 8, wherein thehydrophilic N-vinyl amide monomer is N-vinylpyrrolidone, N-vinylpiperidone, N-vinyl caprolactam, N-vinyl-N-methyl acetamide, N-vinylformamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl formamide, andmixtures thereof.
 15. The method of claim 14, wherein the polymerizablecomposition further comprises one or more non-silicone vinyliccrosslinking agents.
 16. The method of claim 15, wherein thepolymerizable composition further comprises at least one UV-absorbingvinylic monomer and optionally at least one UV/HEVL-absorbing vinylicmonomer.
 17. The method of claim 16, wherein the polymerizablecomposition further comprises2-[2′-hydroxy-5′-(2-methacryloxyethyl)phenyl)]-2H-benzotriazole(Norbloc) and at least one UV/HEVL-absorbing vinylic monomer selectedfrom the group consisting of2-{2′-Hydroxy-3′-tert-butyl-5-[3′-methacryloyloxypropoxy]phenyl}-2H-benzotriazole,2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-5-methoxy-2H-benzotriazole(UV13),2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-5-chloro-2H-benzotriazole(UV28),2-[2′-Hydroxy-3′-tert-butyl-5′-(3′-acryloyloxypropoxy)phenyl]-5-trifluoromethyl-2H-benzotriazole(UV23), and combinations thereof.
 18. The method of claim 4, wherein thepolymerizable composition further comprises one or more hydrophilicacrylic monomers selected from the group consisting of N,N-dimethyl(meth)acrylamide, (meth)acrylamide, N-hydroxylethyl (meth)acrylamide,N-hydroxypropyl (meth)acrylamide, hydroxyethyl (meth)acrylate, glycerolmethacrylate (GMA), polyethylene glycol (meth)acrylate having a numberaverage molecular weight of up to 1500, polyethylene glycol C₁-C₄-alkylether (meth)acrylate having a number average molecular weight of up to1500, N-[tris(hydroxymethyl)methyl]-acrylamide, (meth)acrylic acid,ethylacrylic acid, and combinations thereof.
 19. The method of claim 6,wherein the polymerizable composition further comprises one or morehydrophilic acrylic monomers selected from the group consisting ofN,N-dimethyl (meth)acrylamide, (meth)acrylamide, N-hydroxylethyl(meth)acrylamide, N-hydroxypropyl (meth)acrylamide, hydroxyethyl(meth)acrylate, glycerol methacrylate (GMA), polyethylene glycol(meth)acrylate having a number average molecular weight of up to 1500,polyethylene glycol C₁-C₄-alkyl ether (meth)acrylate having a numberaverage molecular weight of up to 1500,N-[tris(hydroxymethyl)methyl]-acrylamide, (meth)acrylic acid,ethylacrylic acid, and combinations thereof.
 20. The method of claim 8,wherein the polymerizable composition further comprises one or morehydrophilic acrylic monomers selected from the group consisting ofN,N-dimethyl (meth)acrylamide, (meth)acrylamide, N-hydroxylethyl(meth)acrylamide, N-hydroxypropyl (meth)acrylamide, hydroxyethyl(meth)acrylate, glycerol methacrylate (GMA), polyethylene glycol(meth)acrylate having a number average molecular weight of up to 1500,polyethylene glycol C₁-C₄-alkyl ether (meth)acrylate having a numberaverage molecular weight of up to 1500,N-[tris(hydroxymethyl)methyl]-acrylamide, (meth)acrylic acid,ethylacrylic acid, and combinations thereof.